Chemical Engineering / Kimya Mühendisliği

Permanent URI for this collectionhttps://hdl.handle.net/11147/14

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  • Article
    Citation - WoS: 4
    Citation - Scopus: 3
    Atomic-Scale Insights Into Carbon Dioxide Hydrogenation Over Bimetallic Iron-Cobalt Catalysts: a Density Functional Theory Study
    (MDPI, 2023) Tuncer, Dilan; Kızılkaya, Ali Can
    The conversion of carbon dioxide to fuels and chemicals is a promising long-term approach for mitigating CO2 emissions. Despite extensive experimental efforts, a fundamental understanding of the bimetallic catalytic structures that selectively produce the desired products is still lacking. Here, we report on a computational surface science approach into the effect of the Fe doping of Co(111) surfaces in relation to CO2 hydrogenation to C1 products. Our results indicate that Fe doping increases the binding strength of surface species but slightly decreases the overall catalytic activity due to an increase in the rate-limiting step of CO dissociation. FeCo(111) surfaces hinder hydrogenation reactions due to lower H coverages and higher activation energies. These effects are linked to the Lewis basic character of the Fe atoms in FeCo(111), leading to an increased charge on the adsorbates. The main effect of Fe doping is identified as the inhibition of oxygen removal from cobalt surfaces, which can be expected to lead to the formation of oxidic phases on bimetallic FeCo catalysts. Overall, our study provides comprehensive mechanistic insights related to the effect of Fe doping on the catalytic behavior and structural evolution of FeCo bimetallic catalysts, which can contribute to the rational design of bimetallic catalysts.
  • Article
    Citation - WoS: 6
    Citation - Scopus: 9
    Mechanistic Insights Into the Effect of Sulfur on the Selectivity of Cobalt-Catalyzed Fischer–tropsch Synthesis: a Dft Study
    (MDPI, 2022) Dağa, Yağmur; Kızılkaya, Ali Can
    Sulfur is a common poison for cobalt-catalyzed Fischer–Tropsch Synthesis (FTS). Alt-hough its effects on catalytic activity are well documented, its effects on selectivity are controversial. Here, we investigated the effects of sulfur-covered cobalt surfaces on the selectivity of FTS using density functional theory (DFT) calculations. Our results indicated that sulfur on the surface of Co(111) resulted in a significant decrease in the adsorption energies of CO, HCO and acetylene, while the binding of H and CH species were not significantly affected. These findings indicate that sulfur increased the surface H/CO coverage ratio while inhibiting the adsorption of carbon chains. The elementary reactions of H-assisted CO dissociation, carbon and oxygen hydrogenation and CH coupling were also investigated on both clean and sulfur-covered Co(111). The results indicated that sulfur decreased the activation barriers for carbon and oxygen hydrogenation, while increasing the barriers for CO dissociation and CH coupling. Combining the results on elementary reactions with the modification of adsorption energies, we concluded that the intrinsic effect of sulfur on the selectivity of cobalt-catalyzed FTS is to increase the selectivity to methane and saturated short-chain hy-drocarbons, while decreasing the selectivity to olefins and long-chain hydrocarbons.